Recent progress on nickel phthalocyanine-based electrocatalysts for CO2 reduction.

The electrocatalytic reduction of CO2 to high-value fuels by renewable electricity is a sustainable strategy, which can substitute for fossil fuels and circumvent climate changes induced by elevated CO2 emission levels, making the rational design of versatile electrocatalysts highly desirable. Among all the electrocatalytic materials used in the CO2 reduction reaction, nickel phthalocyanine (NiPc)-based electrocatalysts have attracted considerable attention recently because of their high CO selectivity and catalytic activity. Herein, we review the latest advances in CO2 electroreduction to CO catalyzed by immobilized NiPc and its derivatives on diverse surfaces. Specific strategies, the structure-performance relationship and the CO2-to-CO reaction mechanism of these NiPc-based electrocatalysts are analyzed. Future opportunities and challenges for this series of powerful heterogeneous electrocatalysts are also highlighted.

Thermodynamic Model for Hydrogen Production from Rice Straw Supercritical Water Gasification.

Supercritical water gasification (SCWG) technology is highly promising for its ability to cleanly and efficiently convert biomass to hydrogen. This paper developed a model for the gasification of rice straw in supercritical water (SCW) to predict the direction and limit of the reaction based on the Gibbs free energy minimization principle. The equilibrium distribution of rice straw gasification products was analyzed under a wide range of parameters including temperatures of 400-1200 °C, pressures of 20-50 MPa, and rice straw concentrations of 5-40 wt%. Coke may not be produced due to the excellent properties of supercritical water under thermodynamic constraints. Higher temperatures, lower pressures, and biomass concentrations facilitated the movement of the chemical equilibrium towards hydrogen production. The hydrogen yield was 47.17 mol/kg at a temperature of 650 °C, a pressure of 25 MPa, and a rice straw concentration of 5 wt%. Meanwhile, there is an absorptive process in the rice straw SCWG process for high-calorific value hydrogen production. Energy self-sufficiency of the SCWG process can be maintained by adding small amounts of oxygen (ER < 0.2). This work would be of great value in guiding rice straw SCWG experiments.

RuSe2 and CoSe2 Nanoparticles Incorporated Nitrogen-Doped Carbon as Efficient Trifunctional Electrocatalyst for Zinc-Air Batteries and Water Splitting.

The development of affordable, highly active, and stable trifunctional electrocatalysts is imperative for sustainable energy applications such as overall water splitting and rechargeable Zn-air battery. Herein, we report a composite electrocatalyst with RuSe2 and CoSe2 hybrid nanoparticles embedded in nitrogen-doped carbon (RuSe2CoSe2/NC) synthesized through a carbonization-adsorption-selenylation strategy. This electrocatalyst is a trifunctional electrocatalyst with excellent hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and oxygen reduction reaction (ORR) activities. An in-depth study of the effect of Se on the electrocatalytic process was conducted. Notably, the incorporation of Se moderately adjusted electronic structure of Ru and Co, enhancing all three types of catalytic performance (HER, η10 = 31 mV; OER, η10 = 248 mV; ORR, E1/2 = 0.834 V) under alkaline condition with accelerated kinetics and improved stability. Density functional theory (DFT) calculation reveals that the (210) crystal facet of RuSe2 is the dominant HER active site as it exhibited the lowest ΔGH* value. The in situ Raman spectra unravel the evolution process of the local electronic environment of Co-Se and Ru-Se bonds, which synergistically promotes the formation of CoOOH as the active intermediate during the OER. The superior catalytic efficiency and remarkable durability of RuSe2CoSe2/NC as an electrode for water splitting and zinc-air battery devices demonstrate its great potential for energy storage and conversion devices.

Supercritical CH3OH-Triggered Isotype Heterojunction and Groups in g-C3N4 for Enhanced Photocatalytic H2 Evolution.

The structure tuning of bulk graphitic carbon nitride (g-C3N4) is a critical way to promote the charge carriers dynamics for enhancing photocatalytic H2-evolution activity. Exploring feasible post-treatment strategies can lead to effective structure tuning, but it still remains a great challenge. Herein, a supercritical CH3OH (ScMeOH) post-treatment strategy (250-300 °C, 8.1-11.8 MPa) is developed for the structure tuning of bulk g-C3N4. This strategy presented advantages of time-saving (less than 10 min), high yield (over 80%), and scalability due to the enhanced mass transfer and high reactivity of ScMeOH. During the ScMeOH post-treatment process, CH3OH molecules diffused into the interlayers of g-C3N4 and subsequently participated in N-methylation and hydroxylation reactions with the intralayers, resulting in a partial phase transformation from g-C3N4 into carbon nitride with a poly(heptazine imide)-like structure (Q-PHI) as well as abundant methyl and hydroxyl groups. The modified g-C3N4 showed enhanced photocatalytic activity with an H2-evolution rate 7.2 times that of pristine g-C3N4, which was attributed to the synergistic effects of the g-C3N4/Q-PHI isotype heterojunction construction, group modulation, and surface area increase. This work presents a post-treatment strategy for structure tuning of bulk g-C3N4 and serves as a case for the application of supercritical fluid technology in photocatalyst synthesis.

Sulfur migration mechanism of pig manure in supercritical water: A combined experimental and DFT study.

Pig manure (PM) is a high concentration organic waste rich in sulfur, and its biofuel contains various sulfur-containing pollutants, which reduces the safety of the products. Supercritical water (SCW) can dissolve most organic matter, which is a technology worthy of further study. In order to reduce sulfur pollution in the process of PM resource utilization and better control the conversion path of sulfur, it is necessary to explore the migration mechanism of sulfur in the whole PM-SCW gasification process. The experimental results indicated that H2S was the only gaseous product. Only inorganic compounds (S2-, S2O32- and SO42-) were detected in the liquid. Sulfur in the solid mainly included thiol/thioether, thiophene and sulfone. The influence of different reaction conditions (temperature, residence time, PM concentration and catalysts) on sulfur migration was studied in a batch reactor. It was worth noting that the catalysts had a significant effect on H2S absorption. The lowest H2S yield was 3.2 * 10-4 mol/kg and more than 70% of the sulfur was distributed in the liquid under the condition of addition of K2CO3. While, the RTH2110 fixed most of the sulfur of PM (the maximum value reached 50.94%) in the solid. Thus, adding the catalysts flexibly can choose composition of the products. Furthermore, six possible pathways of sulfur migration in the solid were designed and the kinetic parameters were calculated by density functional theory (DFT). The results provided a basis for controlling sulfur in PM. Subsequently, the sulfur migration pathways during PM-SCW gasification process were comprehensively summarized through the combination of experiment and DFT. It provided a method for sulfur treatment in PM, which had guiding significance for the realization of pollution-free treatment of PM.

Pilot composite tubular bioreactor for outdoor photo-fermentation hydrogen production: From batch to continuous operation.

A novel 70 L composite tubular photo-bioreactor was constructed, and its photo-fermentation hydrogen production characteristics of batch and continuous modes were investigated with glucose as the substrate in an outdoor environment. In the batch fermentation stage, the hydrogen production rate peaked at 37.6 mL H2/(L·h) accompanied by a high hydrogen yield of 7 mol H2/mol glucose. The daytime light conversion efficiency is 4 %, with 37 % of light energy from the sun. An optimal hydraulic retention time of 5 d was identified during continuous photo-fermentation. Under this condition, the stability of the cell concentration is maintained and more electrons can be driven to the hydrogen generation pathway while attaining a hydrogen production rate of 20.7 ± 0.9 mL H2/(L·h). The changes of biomass, volatile fatty acids concentration and ion concentration during fermentation were analyzed. Continuous hydrogen production by composite tubular photo-bioreactor offers new ideas for the large-scale deployment of photobiological hydrogen production.

Light energy utilization and microbial catalysis for enhanced biohydrogen: Ternary coupling system of triethanolamine-mediated Fe@C-Rhodobacter sphaeroides.

This study investigated the mediating effect of Triethanolamine on Fe@C-Rhodobacter sphaeroides hybrid photosynthetic system to achieve efficient biohydrogen production. The biocompatible Fe@C generates excited electrons upon exposure to light, releasing ferrum for nitrogenase synthesis, and regulating the pH of the fermentation environment. Triethanolamine was introduced to optimize the electron transfer chain, thereby improving system stability, prolonging electron lifespan, and facilitating ferrum corrosion. This, in turn, stimulated the lactic acid synthetic metabolic pathway of Rhodobacter sphaeroides, resulting in increased reducing power in the biohybrid system. The ternary coupling system was analyzed through the regulation of concentration, initial pH, and light intensity. The system achieved the highest total H2 production of 5410.9 mL/L, 1.29 times higher than the control (2360.5 mL/L). This research provides a valuable strategy for constructing ferrum-carbon-based composite-cellular biohybrid systems for photo-fermentation H2 production.

Mechanistic insights and catalytic enhancement of phenolic wastewater supercritical water gasification: A combined experiment and density functional theory study.

Supercritical water gasification technology provides a favorable technology to achieve pollution elimination and resource utilization of phenolic wastewater. In this study, the reaction mechanism of phenolic wastewater supercritical water gasification was investigated using a combination of experimental and computational methods. Five reaction channels were identified to elucidate the underlying pathway of phenol decomposition. Importantly, the rate-determining step was found to be the dearomatization reaction. By integrating computational and experimental analyses, it was found that phenol decomposition via the path with the lowest energy barrier generates cyclopentadiene, featuring a dearomatization barrier of 70.97 kcal/mol. Additionally, supercritical water plays a catalytic role in the dearomatization process by facilitating proton transfer. Based on the obtained reaction pathway, alkali salts (Na2CO3 and K2CO3) are employed as a catalyst to diminish the energy barrier of the rate-determining step to 40.00 kcal/mol and 37.14 kcal/mol. Alkali salts catalysis significantly improved carbon conversion and pollutant removal from phenolic wastewater, increasing CGE from 58.44% to 93.55% and COD removal efficiency from 94.11% to 99.79%. Overall, this study provides a comprehensive understanding of the decomposition mechanism of phenolic wastewater in supercritical water.

Copper Vacancy and LSPR-Activated MXene Synergistically Enabling Selective Photoreduction CO2 to Acetate.

Photocatalytic CO2 conversion towards C2+ fuels is a promising technology for simultaneously achieving carbon neutrality and alleviating the energy crisis. However, this strategy is inefficient due to the difficulty of both multi-electron transfer and C-C coupling during C2+ formation. In this work, CuInS2/MXene heterostructure with Cu vacancy is rationally designed by in situ hydrothermal synthesis. The VCu-CuInS2/MXene heterostructure has a suitable band structure and tight interface contact. Catalytic performances under different testing conditions, in situ spectroscopy, and COMSOL simulation reveal that LSPR-activated MXene promotes the formation of crucial intermediate CH2* and triggers the C-C coupling process under near-infrared light, as the key to acetate. Moreover, in situ XPS analysis, DFT calculations, and photoelectrochemical characterizations unveil that copper vacancy can promote charge transfer from CuInS2 to MXene and boost local electron aggregation on the MXene, further enhancing the photocatalytic efficiency and selectivity of C2 products. Contributing to the synergistic effect of copper vacancy and plasmonic MXene, VCu-CuInS2/MXene achieved excellent CO2RR activity with an acetate evolution rate of 250.0 µmol/h/g and a selectivity of 97.5 % under the full spectrum irradiation, which is 38.8 and 3.3 times higher than that of VCu-CuInS2 and CuInS2/MXene, respectively.

Decoupled electrolysis for hydrogen production and hydrazine oxidation via high-capacity and stable pre-protonated vanadium hexacyanoferrate.

Decoupled electrolysis for hydrogen production with the aid of a redox mediator enables two half-reactions operating at different rates, time, and spaces, which offers great flexibility in operation. Herein, a pre-protonated vanadium hexacyanoferrate (p-VHCF) redox mediator is synthesized. It offers a high reversible specific capacity up to 128 mAh g-1 and long cycling performance of 6000 cycles with capacity retention about 100% at a current density of 10 A g-1 due to the enhanced hydrogen bonding network. By using this mediator, a membrane-free water electrolytic cell is built to achieve decoupled hydrogen and oxygen production. More importantly, a decoupled electrolysis system for hydrogen production and hydrazine oxidation is constructed, which realizes not only separate hydrogen generation but electricity generation through the p-VHCF-N2H4 liquid battery. Therefore, this work enables the flexible energy conversion and storage with hydrogen production driven by solar cell at day-time and electricity output at night-time.

Directional transformation and migration pathways of nitrogen during pig manure supercritical water gasification.

Nitrogen is a valuable nutrient element in pig manure. This work focuses on investigating the distribution, directional transformation, and migration pathways to facilitate the recovery of nitrogen from supercritical water gasification products. Results indicated that no nitrogen-containing gas was detected and 12.65 % of nitrogen remained in solid products. 82.49 % of nitrogen migrated into liquid products, which are predominated by ammonia. Catalysts were employed to promote the conversion of solid nitrogen to liquid nitrogen and organic nitrogen to ammonia. Finally, 85 % of nitrogen is enriched into liquid products and ammonia predominated the liquid nitrogen. The percentage of ammonia increased to 97.51 % at 620 °C in the presence of potassium carbonate. The migration pathways indicated that nitrogen was transformed into ammonia by various intermediates such as indole. The rest of the nitrogen remained in solid products with stable quaternary-nitrogen. These findings provide valuable insights into nitrogen management and recovery.

dz2 Band Links Frontier Orbitals and Charge Carrier Dynamics of Single-Atom Cocatalyst-Aided Photocatalytic H2 Production.

The Cu single-atom catalyst (SAC) supported on TiO2 exhibits outstanding efficacy in photocatalytic hydrogen evolution. The precise operational mechanism remains a subject of ongoing debate. The focus resides with the interplay linking heightened catalytic activity, dynamic valence state alterations of Cu atoms, and their hybridization with H2O orbitals, manifested in catalyst color changes. Taking anatase TiO2 (101) as a prototypical surface, we perform ab initio quantum dynamics simulation to reveal that the high activity of the Cu-SAC is due to the quasi-planar coordination structure of the Cu atom after H2O adsorption, allowing it to trap photoexcited hot electrons and inject them into the hybridized orbital between Cu and H2O. The observed alterations in the valence state and the coloration can be attributed to the H atom released during H2O dissociation and adsorbed onto the lattice O atom neighboring the Cu-SAC. Notably, this adsorption of H atoms puts the Cu-SAC into an inert state, as opposed to an activating effect reported previously. Our work clarifies the relationship between the high photocatalytic activity and the local dynamic atomic coordination structure, providing atomistic insights into the structural changes occurring during photocatalytic reactions on SACs.

Fermi Level Pinning in Concentrated Light-Induced Band Edge Tuning Maximizes Photocatalytic Solar-to-Hydrogen Efficiency.

Here, we demonstrate a concentrated light-induced band edge tuning effect in photocatalytic hydrogen production. This band movement along with Femi level pinning leads to two distinct catalytic behaviors upon irradiation flux increase. Specifically, the concentration of the light promotes more long-lived carriers bound to the surface electronic states, progressively boosting energy conversion efficiency to a maximum value. Afterward, efficiency diminishes gradually due to poor carrier transfer. This work offers critical insights into efficient and economical photocatalytic hydrogen production.

Growth characteristics and the mass transfer mechanism of single bubble on a photoelectrode at different electrolyte concentrations.

In the photoelectrochemical water splitting reaction, the bubble attached to the working electrode is an essential factor affecting the reaction resistance, current density and gas-liquid mass transfer. An experimental measurement system based on an electrochemical workstation synchronously coupled with a high-speed microscopic camera was proposed and used to systematically study the growth kinetics and mass transfer mechanism of single oxygen bubbles at different electrolyte concentrations (Na2SO4, 0.1-2.0 M) on the TiO2 photoanode surface. Under constant voltage and constant current control conditions, when the electrolyte concentration increases, the bubble detachment diameter and the bubble detachment frequency gradually decrease. The bubble coverage equation expressed in terms of gas evolution efficiency is proposed and is associated with the photocurrent and bubble radius. The average bubble coverage and average gas evolution efficiency decrease when the electrolyte concentration is increased. According to the Sherwood dimensionless number, various mass transfer coefficients during bubble growth were calculated. The results show that the average total mass transfer coefficient is positively correlated with the change trend of the electrolyte concentration, and the mass transfer coefficient of single-phase natural convection is one order of magnitude larger than the mass transfer coefficient of bubble-induced convection. Finally, a conclusion on the transient mass transfer process in the bubble evolution process was obtained, that is, the mass transfer coefficient of single-phase natural convection and the total mass transfer coefficient remain high during the first growth stage, and gradually decrease during the second growth stage. Therefore, regulating the electrolyte concentration can effectively promote the gas-liquid mass transfer in the photoelectrochemical water splitting reaction.

Influence of subatmospheric pressure on bubble evolution on the TiO2 photoelectrode surface.

The increase of reaction resistance caused by bubble nucleation and long-time growth on the surface of the photoelectrode is an important factor that leads to the low efficiency of photoelectrochemical water splitting. In this study, we adopted an electrochemical workstation synchronous with a high-speed microscopic camera system to achieve in situ observation of oxygen bubble behavior on the surface of TiO2 and to study the internal relationship between the geometric parameters of oxygen bubbles and photocurrent fluctuations under different pressures and laser powers. The results indicate that with the decrease of pressure, the photocurrent decreases gradually and the bubble departure diameter increases gradually. In addition, the nucleation waiting stage and the growth stage of bubbles are both shortened. However, the difference between the average photocurrents corresponding to the moment of bubble nucleation and the stable growth stage hardly changes with the pressure. The production rate of gas mass reaches a peak near 80 kPa. In addition, a force balance model suitable for different pressures is constructed. It is found that as the pressure decreases from 97 kPa to 40 kPa, the proportion of the thermal Marangoni force in the Marangoni force decreases from 29.4% to 21.3%, while the proportion of the concentration Marangoni force increases from 70.6% to 78.7%, indicating that the concentration Marangoni force is the main factor affecting the bubble departure diameter under subatmospheric pressure conditions.

Unraveling the Selectivity and Synergistic Mechanism of Cu-Based Alloys for CO2 Reduction.

Understanding the synergistic effect of Cu-based alloys on the adsorption behavior and selectivity of the CO2 reduction reaction is a crucial step toward directional catalyst design. To this end, density functional theory calculations are employed to investigate Cu-based alloys with diverse doping elements and contents. The results show that the scaling relation still holds in the alloy system, and the strategies to improve the selectivity are put forward based on the adsorption strength of *C and *OCHO intermediates. Further, a model combining the adsorption theory and machine learning algorithm is proposed to capture the relationship between the adsorption energy and the geometric environment. It explains that the difference in d-band centers between the doped metals and Cu affects the variation trend of the adsorption strength and reveals that the intermetallic synergistic effect can be quantified by the bonding distance and d orbital radius on both the adsorbate and metal side.

Near-Infrared-Responsive Photocatalytic CO2 Conversion via In Situ Generated Co3O4/Cu2O.

Photocatalytic CO2 conversion to fuels is a promising strategy for achieving global carbon neutrality. However, infrared light, which accounts for ∼50% of the full sunlight spectrum, has not yet been effectively utilized via photocatalysis. Here, we present an approach to directly power photocatalytic CO2 reduction using near-infrared light. This near-infrared light-responsive process occurs on an in situ generated Co3O4/Cu2O photocatalyst with a nanobranch structure. Photoassisted Kelvin probe force microscopy and relative photocatalytic measurements demonstrate the increase of surface photovoltage after illumination by near-infrared light. We also find that Cu(I) on this in situ generated Co3O4/Cu2O could facilitate the formation of a *CHO intermediate, thus enabling a high-performance CH4 production with a yield of 6.5 µmol/h and a selectivity of 99%. Moreover, we perform a practically oriented direct solar-driven photocatalytic CO2 reduction under concentrated sunlight and achieve a fuel yield of 12.5 µmol/h.

Experimental study on supercritical water gasification of oily sludge using a continuous two-step method.

Supercritical water gasification (SCWG) technology can convert oily sludge into hydrogen-rich gas. To achieve high gasification efficiency of oily sludge with a high oil concentration under mild conditions, a two-step method involving a desorption process and a catalytic gasification process using Raney-Ni catalyst was investigated. High oil removal efficiency (99.57%) and carbon gasification efficiency (93.87%) were achieved. The lowest wastewater total organic carbon, oil content, and carbon content in the solid residues were 4.88 ppm, 0.08% and 0.88%, respectively, using a gasification temperature of 600 °C, treatment concentration of 1.11 wt%, gasification time of 70.7 s, and the optimal desorption temperature of 390 °C. The main organic carbon component in the solid residues was cellulose, which is environmentally safe. As the treatment concentration increased, the two-step method outperformed the single-step method. The mechanism for the two-step SCWG of oily sludge was revealed. In the first step, supercritical water is used in the desorption unit to achieve a high oil removal efficiency with few liquid products generated. In the second step, the Raney-Ni catalyst promotes efficient gasification of high-concentration oil at a low temperature. This research provides valuable insights into the effective SCWG of oily sludge at a low temperature.

Solar Hydrocarbons: Single-Step, Atmospheric-Pressure Synthesis of C2 -C4 Alkanes and Alkenes from CO2.

Cobalt ferrite (CoFe2 O4 ) spinel has been found to produce C2 -C4 hydrocarbons in a single-step, ambient-pressure, photocatalytic hydrogenation of CO2 with a rate of 1.1 mmol g-1 h-1 , selectivity of 29.8 % and conversion yield of 12.9 %. On stream the CoFe2 O4 reconstructs to a CoFe-CoFe2 O4 alloy-spinel nanocomposite which facilitates the light-assisted transformation of CO2 to CO and hydrogenation of the CO to C2 -C4 hydrocarbons. Promising results obtained from a laboratory demonstrator bode well for the development of a solar hydrocarbon pilot refinery.

Insights into direct reduction iron using bamboo biomass as a green and renewable reducer: Reduction behavior study and kinetics analysis.

Biochar is a renewable, carbon-neutral energy source that can replace traditional fossil fuels for iron and steel production, so it is of great significance to reduce carbon emissions and reduce pollution. In this paper, the reaction characteristics and kinetics between biomass (bamboo powder) pyrolysis gas, biochar, and iron ore powder are studied by a thermogravimetric analyzer (TG). Comparing the samples with four different C/O ratios (C/O = 0.375, 0.5, 1, 3), it is found that the sample with C/O = 1 can completely reduce hematite. The mass loss process is divided into the following four stages: de-crystal water, hematite to magnetite, magnetite to wustite, and wustite to metallic iron. Among them, the latter three stages are following the kinetic model of random nucleation (n = 1, 2) and three-dimensional diffusion, and the activation energy of the three stages increases and then decreases. Through scanning electron microscopy (SEM), the surface of hematite particles changed from relatively flat to porous and finally the reduced metal iron aggregated, and connected into large pieces. By using online Thermogravimetry-Fourier Transform Infrared Reflection (TG-FTIR), when the reduction temperature is lower than 700 °C, biochar plays a leading role. On the contrary, the CO produced by biochar gasification plays a leading role.